p-phenylenediamine developer containing alkylacylamidoethyl or alkylacylamidoethoxyring substituents



?atented Apr. 8, 1952 p-PHENYLENEDIAMINE DEVELOPER CON- TAININGALKYLACYLAMIDOETHYL 10R AIZKYLACYLAIVHPOETHPX? RING SUB- STITUENTSArnold Weissberger, Dudley B. Glass, and Paul W. Vittum, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporationof New Jersey N i Application March e, 1948, ferial No. 1532 5 26 6Claims. 1 ,This invention relates to photographic developers and moreparticularly to photographic developers containing alkylacylamidoeth'ylor alkylacylamidoethoxy ring substituents.

It is known that photographic developers of the p-phenylenediamine typeare valuable compoundsfor producingiilnglgrain black and whitephotographic images'an'dalso that these compounds, especially when theycontain alkyl substituents on one of the nitrogen atoms, are useful asdevelopers in producing colored photographic images. A seriousdisadvantage of the p-phenylenediamine developers is that they arehighly allergenic, that is, they are poisonous to the human skin and aretherefore somewhat dangerous to use.

The allergenic properties of the p-phenylenediamine developers may beovercome by substituting .a su1fonamide group or an amino sulfonyl groupin the alkyl'group on the nitrogen atom of p-phenyle'nediamine asdescribed in Weissberger U. S. Patent 2,193,015 granted March 12, 1940.'Ihesesubstituted p-phenylenediamine developers, however, aresometimestoo low in developing strength (or reduction potential) so thatit is diflicult to obtain, with them, dye images of suifici'entlyrhighdensity and contrast.

It is-therefore an object oi. the present-invention to provide a newclass of photographic developing agents ofthe p-phenylenediamine type.

A further object is to provide developing agents of thep-phenylenediamine type which produce dye images having the desiredcharacteristics.

These objects are accomplished by the present invention by the use asdeveloping agents of compounds of the followinggeneral formulas:

and

where R is a lower alkyl group such as methyl, ethyl or propyl, B is ,alower alkyl r up, X is the substituted acyl group -SO2R" or' CQ and R isa lower alkyl group.

By lower alkyl group, we mean a methyl, ethyl or propyl group.

Compounds of this class which may be used acording'toour invention areasfollowsf 1. C:Ha\ /C:H|

omqmNHoo on,

3- (B-acetamidoethyl) -4-am ino-N,N-dlethy1aniline 2, C;Ha\ /C1H|CHaCEhNI-ISOzQH:

4-amino-N,N-diethyl-3-(B-methylsulfonamidoethyl)- aniline V 3. CiHt@2136 N .pCmCmNHCQQm 40 Ma thead:dete m e esessg s fle-4-Amino-N;N-diethyl-3-(B-methylsulfonamldoethoxyr v l'. w t. 4 ..:,;V':M: xial. s I

The preparation of our developers may be the residue was distilled underreduced pressure summarized by the following reaction schemes:collecting the fraction that boiled at 120-150/2 N: NO: NO: NH, N r

H: Br; NaCN SnCh CaHd NHKLiq) CH CHaBr OHgCN CHiCN CHICN ickel H omco oHONO Nlci rel CE|CH NH CHICHINHCOCHI CH|CH3NHCOCH| CH CHgNHCOCH:

NO NH:

GIH! CIHI CIH! 01H; CIHI CIHI 2 0 C111:

ems 0,01 HONO H,

---o -o o omomNH, omomNHsmcm cmcmNHs 0.0m Nick omonmnsmcm N O N H:

(as above in 1) 3. CIHI C13] 2 61B;

NK CaHa CaHl aHl CIHI ll 0H ocmomol p C CO 0 v oomonm O ILNHIO H:

O CH: C HQNH] Ha HONO Nickel OCHgCHgNHCOCH: OCHICHZNHCOCHIOOHzCHzNHCOCHI N O NH:

CIHI C2H| 1H: ClHl IHi 1H: CiHl CaHl OCHgCHzNH: OCHICHQNHBOQCHIOCHgCH|NHSO1CH| OCHzCHzNHSOnCH:

NO NH:

The specific compounds illustrated above were mm. This crude product wasredistilled under prepared as follows: reduced pressure collecting theportion that 1. 3-(p-Acetamidoethyl)-4-amino-N.N-dieth- 65 boiled at160-162/l4 mm. This redistilled maylaniline was prepared from3-nitrotoluene by terial was recrystallized from methanol and dried thefollowing series of reactions. in air. Melting point 58-59".

a. 3-Nitr0benzyl Bromide.--3-Nitroto1uene b.3-NitrophenylacetonitriZe.-Sodium cyanide moles) was heated at 135:5"and bromide (5 (1.0 mole) was dissolved in 80 ml. of water. Almoles) wasdropped in during a period of 5 70 cohol (280 ml.) was added and themixture was hours. During this time the reaction mixture cooled to3-Nitrobenzyl bromide (0.8 mole) was exposed to the light of a 200 Wclear bulb. was added and the mixture was stirred and The reactionmixture was cooled, dissolved in warmed slowly to At'this temperaturethe ether and the ether was dried over anhydrous heating was stopped andthe exothermic reacsodium sulfate. The ether was evaporated and tionallowed to proceed. The temperature was diseases not allowed to riseabove 60-65". After the spontaneous reaction was over, the reactionmixture was boiled for 1 hour. The alcohol was removed under reducedpressure and the residue was dissolved in 250 m1. of water plus 300 ml.of ether. The layers were separated, and the ether layer was washed withwater and dried over anhydrous sodium sulfate. The ether was evaporatedand the residue was distilled under reduced pressure collecting thefraction that boiled at 160- 165/3 mm. The product was recrystallizedfrom methanol. Melting point 61-62.

c. 3-AminophenylacetonitriZe.-3 Nitrophenylacetonitrile (0.9 mole) wasadded to a solution of stannous chloride (2.7 moles) in concentratedhydrochloric acid (700 ml.) The temperature of the reaction mixture wasmaintained at 35- 40", by cooling, until the exothermic reactionsubsided. After stirring for 2 hours, the so1u tion was made alkalinewith 2 l. of 40 percent sodium hydroxide solution. This mixture wasdiluted with 1 l. of water and the product extracted with ether. Theether solution was washed with water, dried over anhydrous sodiumsulfate and the ether was evaporated. The residue was: distilled underreduced pressure collecting the fraction that boiled at l3-2-135/-2' d.3-(N,N-Diet-hylamino) phenylacetonitrila A mixture of3-amino-phenylacetonitrile (0.75 mole). alcohol (400 ml.). sodiumcarbonate (1.0 mole), water (100 ml.) and ethyl iodide (1.8 moles) wasboiled under refiux for 6 hours. The alcohol was removed under reducedpressure and the residue was dissolved in a mixture of water (500 ml.)and ether (500 ml.). The ether layer was separated, washed with waterand dried over anhydrous sodium sulfate. The ether was evaporated andthe residue was distilled un der reduced pressure collecting thefraction that boiled at 125-130/2 mm.

e. 3-(p-Aminoethyl)-N,N diethylcmilt'ne.3- (N,N diethylamino)-phenylacetonitrile (0.66 mole) was placed in a high pressure reductionapparatus with liquid ammonia (250 ml.) and methanol (150 ml.)andhydrogenated at 110 in the presence of Raney nickel (10 g.) and ahydrogen pressure of 1500 lbs./in. The product was distilled underreduced pressure collecting the fraction that boiled at 148-150f/1.0 mm.

,f. 3-08 Acetamidoethyl)-4-amino-N;N-diethylaniline. 3 -(fi-Amino-ethyl)N,N diethylani line (0.39 mole) was added with stirring andcooling to 40ml. of acetic anhydride. The mixture was kept below a temperature of 50during the addition and thenwas heated on the steambath for 30 minutes.After cooling. the solutionwas stirred with 400 ml. of water until the:excess. acetic anhydride had decomposed. The solution was made; acidwith 100 m1. of concentrated hydrochloric acid. cooled to. 0",v andnitrosated by the. addition of a solution of 28 g. of sodium nitrite in50, ml. of water. The nitrite. was: added during a period. of 1 hour.Stirring, was. 6011. tinued for 1 hour longer at 0. This solution was:further: acidified by the: addition of 8.0. ml. ofconcentrated.hydrochloric acid and the. nitroso compound was reduced with. 65 g; ofzincv dust. The zinc-dust was added in portions, with stirring, while.the temperature of the reaction mixture was, maintained at :5";Theexcess zinc dust was filtered. off. and the solution, wasmadealkalinewith 400 ml. of ammonium; hydroxide. The diamine was extracted with 600of chloroform. The chloroform. solutions. was washed with water anddried over anhydrous sodium sulfate. The chloroform was removed under-roduced pressure and the diamine was distilled under reduced pressure. Theportion that boiled at 190-l95 at 1. mm. was collected as the de siredproduct. 2. i-Amino N,N-diethyl' 3-(B-methylsulfon amidoethy-l) anilinewas prepared from 3 (5- aminoethyl)-N,N-diethylaniline by the renowingmethod.

A mixture of 3-(5 aminoethyD-NN-diethyl aniline (0.36 mole) and water(150 ml.) was cooled to 15 and stirred vigorously while meth'anesu-lfonyl chloride (0.41 mole) was dropped in during the course of 30minutes. After each fifth of the methanesulfonyl chloride had beenadded, one-fifth of a solution of sodium hydroxide (0.41 mole) in water(50 ml.) was added. The temperature was held at 15-20" throughouttheaddition. The mixture was stirred for-2 hours at room temperature andthen extracted with chloroform. The chloroform solution was washed withwater, dried over anhydrous sodium sulfate and the chloroform wasevaporated under reduced pressure. solved in a mixture of ml. ofconcentrated hydrochloric acid and 100 ml. of water, and n-itrosated at0 by the addition of 22.5 g. of solid sodium nitrite during a period of1 hour. The mixture was stirred for 1 hour at 0-5 and then made alkalinewith ammonium hydroxide. The mixture was stirred thoroughly and theaqueous portion was decanted from the gummy product. The gum was washedwith water ana'd dissolved in a mixture of 166 ml. of concentratedhydrochloric acid and 400ml. of water. This mixture was cooled to 15 andzinc dust (1' mole) was added in portions with stirring, keeping thetem-- perature below 20. The excess zinc was re moved by" filtration andthe filtrate made alkaline with ammonium hydroxide. The diamine wasextracted with chloroform. The chloroform solution was washed withwater, dried over anhydrous sodium sulfate and the chloroform wasremoved under reduced pressure. The residue was distilled under reducedpressure. The fraction that boiled at 21 5-220 1 mm. was collected aspure product.

3. 3- 9 Acetamidoethoxy) --4 amino N,N- diethylaniline was prepared bythe followingseries of reactions.

at. 3- (B Chloroathory) --N,N-diethylaniZine.-- A solution of 80 a; ofsodium hydroxidein 21. of water was placed in a. flask and melted 3-(N,N

diethylamino)pheno1 (3 moles) was added with stirring. Ethylenedichloride (amen): was added and. the mixture was heated on a steam bathfor l9hours with stirring; At the end ofthis period the mixture wascooled and ml. of 40% 60- dium hydroxide solution was stirred in. Thesol'u-- ti'on was extracted twice with ether. The-ether solution waswashed with water, dried over an precipitate was" removed by filtration;washed with alcohoiand' recrystallized from amixture-of The residue wasdis- 7 850 ml. of 3A and 760 ml. of ethylacetate. The product melted at127-129".

0. 3 8 Aminoethoxy) N,N diethylani- Zine.A mixture of N,N-diethyl-3-(B-phthali midoethoxy) aniline (0.43 mole), 85% hydrazine (0.43 mole) and300 ml. of alcohol was boiled under reflux for 30 minutes. The mixturewas cooled somewhat and 140 ml. of concentrated hydrochloric acid wasadded. The mixture was then boiled under reflux for 30 minutes cooledand diluted with 750 ml. of water. The hydrazide was filtered oil andthe filtrate was concentrated under reduced pressure until the alcoholhad been removed. The residue was made alkaline with ammonium hydroxide.The amine was extracted with ether. The ether solution was dried overanhydrous sodium sulfate and the ether was evaporated. The residue wasdistilled under reduced pressure. The product boiled at 135142 at 2 mm.

d. 3 (13 Acetamidoethory) N,N diethylaniline.3 8 Aminoethoxy) N,Ndiethylaniline (0.07 mole) was added to 15 ml. of acetic anhydride andthe solution was heated on a steam bath for 30 minutes. The solution wasstirred with 70 ml. of water until the excess anhydride had decomposedand then was concentrated to a thick syrup under reduced pressure. Thesyrup was dissolved in 150 ml. of boiling ligroin. The ligroin solutionwas filtered while still hot and allowed to cool. The crystals wereremoved by filtration and dried in air. Melting point 66.5 67".

6. 3 (,8 Acetamz'doethomy) N,N diethyl 4 nitrosoam'lz'na-ii (pAcetamidoethoxy) N,N-diethylaniline (0.07 mole) was dissolved in 140 ml.of water and 21 ml. of concentrated hydrochloric acid. The solution wascooled to and nitrosated with a solution of 5.0 g. of sodium nitrite in35 ml. of water. After standing at, 0 for 20 minutes the reactionmixture was made alkaline with ammonium hydroxide and the nitrosocompound was extracted with chloroform. The chloroform solution wasdried over anhydrous sodium sulfate and then the chloroform was removedunder reduced pressure keeping the temperature of the nitroso compoundat 2025. The nitroso compound after recrystallized from benzene meltedat 124124.5.

,f. 3 (p Acetamidoethowy) 4 amino -N,N

diethylamflina-3 (,B Acetamidoethoxy) N,N-

diethyl-i-nitrosoaniline (0.06 mole) and 50 m1. of absolute alcohol wereplaced in a Parr hydrogenation apparatus and reduced in the presence ofRaney nickel at a temperature of 60 and a hydrogen pressure of 3atmospheres. The catalyst was removed by filtration and the alcohol wasevaporated under reduced pressure. The residue was distilled underreduced pressure. The portion that boiled at 112-114" at 1 mm. wasdiluted with 25 ml. of petroleum ether. After standing at 0 for 16hours, the product was filtered off and dried in a vacuum desiccator.Melting point 50-51.

4. 4 Amino N,N diethyl 3 (5 methylsulfonamidoethoxy)-aniline wasprepared from 3-(B-aminoethoxy) -N,N-diethylaniline by the followingmethod.

- a. N,N Diethyl 3 (,3 methylsulfonamidoethomy)aniZine.-A mixture of 3(,3 aminoethoxy) -N,N-diethy1aniline (0.1 mole) and 40 ml. of water wascooled to 15-20 and stirred while 9 m1. of methanesulfonyl chloride wasadded slowly. After each quarter of theacid chloride hadbeen added,one-fourth of a solution of 4.5 g. of sodium hydroxide in 15 m1. ofwater was added.

8 The temperature of the reaction mixture was maintained at 15-20 duringthe reaction. After stirring at 20 for two hours, the precipitate wasremoved by filtration and recrystallized from 110 ml. of aqueousalcohol. Alter drying in air, the product melted at 7 0-72".

I). N,N Diethyl 3 (p methylsuljonamzdoethoccy) 4 nitrosoamline.-Asolution of N,N- diethyl 3 (,8 methylsulfonamidoethoxy) aniline (0.058mole) in ml. of water and 17 ml.

of concentrated hydrochloric acid was cooled to 0 and nitrosated by theaddition of a' solution of 4.1 g. of sodium nitrite in 15 ml. of water.The solution was stirred at 0 for 20 minutes, diluted with 50 ml. ofwater and made alkaline with ammonium hydroxide. The precipitate wasremoved by filtration and recrystallized from 100 ml. of 50% aqueousalcohol. The product was dried in air.

0. 4-Amino-N,N-diethyl 3 (B-methylsuljon amidoethozty) aniZine.-N,NDiethyl 3 (B- methylsulfonamidoethoxy) 4 nitrosoanlline (0.0364 mole)and 75 ml. of absolute alcohol were placed in a Parr hydrogenationapparatus and reduced in the presence of Raney nickel at a temperatureof and a hydrogen pressure of 3 atmospheres. The catalyst was removed byiiitration and the filtrate was concentrated to a syrup under reducedpressure. The residue was recrystallized from aqueous alcohol. Theproduct, dried in a vacuum desiccator, melted at 89-91.

When used for the formation of colored photo A. 4 Amino N,N diethyl 3(,8 methylsulfonamidoethyl) aniline grams 2.5 Sodium sulfite do 2 Sodiumcarbonate do 30 Potassium bromide do 2 Water to 1 liter B. Coupler(o-phenylphenol) grams 2 Sodium hydroxide l0 solution) cc.. 20 For use,B is added to A.

The developing agents described in the present application may be usedto form photographic images by development of exposed silver halidecontained. in the usual gelatin carrier or in carriers such ascollodion, water-permeable cellulose ester or water-permeable syntheticresins. Our

developing agents may be used with photographic films containing thecoupler in the emulsion layer as described in Mannes and Godowsky U. S.Patent 2,304,940, granted December 15, 1942 or Jelley and Vittum'U. S.Patent 2,322,027, granted June 15, 1943; When used in this way, adevelopingsolution similar in. composition to Part A in the aboveexample is suitable.

It will be understood that the examples included herein are illustrativeonly and that our invention is to be taken as limited only by the scopeof the appended claims.

We claim: .1. A photographic silver halide developing solutioncomprising as the developing agent a compound of the group consisting ofCHzCHzNHX and O CHICBINHX where R and R are lower alkyl groups, X isselected from the class consisting of --SO2R" and COR" groups, and R" isa lower alkyl group, and a compound which couples with the oxidationproduct of the developing agent to form a colored image.

2. A photographic silver halide developing solution which contains, as adeveloping agent, a substantial amount of 3-(fi-acetamidoethyl) -4-amino N,N diethyla-niline, and a compound which couples with theoxidation product of the developing agent to form a colored image.

3., A photographic silver halide developing solution which contains, asa developing agent, a substantial amount of4-amino-N,N-diethyl-3-(flmethyl-sulfonamidoethyl) -aniline. and a.compound which couples with the oxidation product of the developingagent to form a colored image.

4. A photographic silver halide developing solution which contains, as adeveloping agent, a substantial amount of 3-(p-acetamidoethoxy) -4amino-N,N-diethylaniline, and a compound which couples with theoxidation product of the developing agent to form a colored image.

5, A silver halide developing solution for producing a coloredphotographic image comprising a developing agent having the formula:

where R and R. are lower alkyl groups, X is selected from the classconsisting of SO:R" and -COR" groups, and R" is a lower alkyl group, anda compound which couples with the oxidation product of the developingagent to form a colored image.

6. A silver halide developing solution for producing a coloredphotographic image comprising a developing agent having the formula:

REFERENCES orrEn The following references are of record in the. file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,193,015 Weissberger Mar. 12,1940 2,304,953 Peterson Dec. 15, 1942 2,414,491 Tulagin Jan. 21, 19472,449,919 Weissberger Sept. 21, 1948

1. A PHOTOGRAPHIC SILVER HALIDE DEVELOPING SOLUTION COMPRISING AS THEDEVELOPING AGENT A COMPOUND OF THE GROUP CONSISTING OF